WO2025001889A1 - 一种Co基有机配位纳米颗粒及其制备方法、光刻胶组合物及其应用 - Google Patents

一种Co基有机配位纳米颗粒及其制备方法、光刻胶组合物及其应用 Download PDF

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WO2025001889A1
WO2025001889A1 PCT/CN2024/099422 CN2024099422W WO2025001889A1 WO 2025001889 A1 WO2025001889 A1 WO 2025001889A1 CN 2024099422 W CN2024099422 W CN 2024099422W WO 2025001889 A1 WO2025001889 A1 WO 2025001889A1
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Prior art keywords
based organic
acid
organic coordination
photoresist composition
acetate
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English (en)
French (fr)
Inventor
徐宏
何向明
胡子昱
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Beijing Vfortune New Energy Power Technology Development Co Ltd
Tsinghua University
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Beijing Vfortune New Energy Power Technology Development Co Ltd
Tsinghua University
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Priority to JP2025507871A priority Critical patent/JP2025528818A/ja
Priority to KR1020257005365A priority patent/KR20250040688A/ko
Publication of WO2025001889A1 publication Critical patent/WO2025001889A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/76—Patterning of masks by imaging
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the invention relates to the technical field of photoresists, and in particular to Co-based organic coordination nanoparticles and a preparation method thereof, a photoresist composition and an application thereof.
  • Photoresist refers to a corrosion-resistant thin film material whose solubility changes when exposed to ultraviolet light, electron beam, particle beam, extreme ultraviolet (EUV) or soft x-rays.
  • EUV extreme ultraviolet
  • photolithography technology is also constantly developing, from I-line, G-line, deep ultraviolet (DUV), 193nm, immersion 193nm to extreme ultraviolet lithography, electron beam lithography and other fine processing methods. After the photoresist film is exposed and developed to form a photolithographic pattern, it will be dry or wet etched.
  • Etching resistance is a very important evaluation index of photoresist. Excellent etching resistance can ensure that the photoresist can protect the substrate surface from damage during the etching process, effectively simplify the etching process, and greatly improve the yield of the finished etching product.
  • Photoresists have complex components, including photoresist resin, photosensitive agent, leveling agent, stabilizer, dispersant, thickener and solvent, etc.
  • the production process is cumbersome and the control process requirements for the ratio and purity are extremely high.
  • traditional photoresists are mostly macromolecular polymers and contain many functional additives, their complex components lead to a wide distribution of photoresist sizes, with components of various sizes, and some size conformations can reach 10nm to 20nm, making the size of photoresist patterns difficult to control and may produce many defects.
  • their scope of use is greatly affected by the wavelength of the light source, and different photoresists are required to match different light sources.
  • metal oxide photoresists have become a research hotspot, and metal oxide photoresists have become a feasible choice for EUV or electron beam exposure of extremely fine patterns.
  • Zn-based nano-organic ligand photoresists are metal oxide organic ligand systems studied by the applicant in the early stage, and their photolithography effects have also been verified in practice. Co and Zn are close in position in the periodic table and have similar properties, so they have the potential to be used as photoresists.
  • Co-based nano-organic ligand photoresists there are no reports on Co-based nano-organic ligand photoresists.
  • the present invention conducts in-depth research on this material system and synthesizes a Co-based nano-organic photoresist composition with good lithography effect.
  • the present invention provides a novel Co-based organic coordination nanoparticle and a preparation method thereof, a photoresist composition containing the same and application thereof.
  • the present invention provides a Co-based organic coordination nanoparticle, the general formula of which is: Co m R n Q x My N z , wherein:
  • Co is two ions, divalent Co and trivalent Co; m, n, and x are all greater than 0, and y and z are greater than or equal to 0;
  • R can be selected from
  • Q may be selected from imidazole and its derivatives
  • M is a carboxylic acid
  • N is crystal water
  • the size of the Co-based organic coordination nanoparticle crystal is 1nm-5nm.
  • Co-based organic coordination nanoparticles may have the following structure:
  • Co 2 (C 7 H 7 COO) 4 (CH 3 C 2 N 2 H 3 ) 2 nanoparticles were prepared by the following method:
  • the molar ratio of the m-toluic acid or benzoic acid to cobalt acetate is in the range of 1:2 to 2:1
  • the molar ratio of the m-toluic acid or benzoic acid, cobalt acetate and 1-methylimidazole is in the range of 1:1:(1 to 3).
  • the organic solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, tetrahydrofuran, methanol, ethanol, and propanol.
  • the stirring temperature is controlled at 25-125°C, preferably 30-100°C, more preferably 30-80°C; the rotary evaporation pressure range is controlled at 70-140mBar, preferably 70-120mBar, more preferably 80-100mBar; at the same time, the rotary evaporation temperature is controlled at 30-45°C, preferably 30-40°C.
  • the invention also provides a photoresist composition, comprising the Co-based organic coordination nanoparticles.
  • the above-mentioned photoresist composition further includes a photoinitiator and an organic dispersing solvent, wherein the photoinitiator preferably occupies 0.5wt%-10wt% of the composition, and the nanoparticles preferably occupy 3wt%-20wt% of the composition.
  • the photoinitiator is selected from any one or more of N-hydroxynaphthaleneimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalene disulfonic acid, tert-butylphenyl iodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.
  • the organic dispersing solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.
  • the solvent is preferably ethyl acetate.
  • the present invention also provides a method for forming a photolithographic pattern, using the above-mentioned photoresist composition, dripping the photoresist composition onto a substrate by spin coating, heating it on a hot stage, then exposing it with an electron beam or mid-ultraviolet, deep ultraviolet, or extreme ultraviolet, and developing it with a developer.
  • the spin coating speed is further controlled at 1500-2500 rpm; the heating temperature of the hot stage is controlled at 50-80° C., and the heating time is controlled at 40-120 s.
  • the exposure dose is 50 mJ/cm 2 to 500 mJ/cm 2 , and preferably the exposure dose is 150 mJ/cm 2 to 300 mJ/cm 2 .
  • the developing time may be selected to be 3-10s, preferably 3s, 5s, or 7s.
  • the developer is selected from a mixture of any one or more of decahydronaphthalene, tetrahydronaphthalene, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is room temperature or 20°C to 50°C.
  • the thickness of the pre-film layer after removing the organic dispersion solvent may be 10 nm to 100 nm.
  • the thickness of the pre-film layer may be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, 90 nm to 100 nm.
  • the substrate is selected from a silicon plate.
  • Other substrates that are insoluble in the developer can also be selected according to actual needs.
  • the above nanoparticles are used in the field of photoresists, especially in the field of electron beam, mid-ultraviolet, deep ultraviolet, extreme ultraviolet Regarding the mask, deep ultraviolet and longer wavelength light sources are transmission masks, extreme ultraviolet is a reflection mask, and the electron beam is exposed according to the pattern set by the software.
  • the Co-based organic coordination nanoparticles obtained by the present invention have a special structure, and under illumination conditions, can interact with a photoinitiator, change the polarity of the material, and agglomerate, causing the solubility of the Co-based organic coordination nanoparticles to change before and after illumination. Due to these characteristics, the Co-based organic coordination nanoparticles are used as photoresist components, and the solubility of the photosensitive part and the light-shielding part of the photoresist in the developer can be different.
  • the photosensitive part agglomerates in the developer and the solubility is reduced, while the light-shielding part does not agglomerate and dissolves in the developer, so that the non-exposed area can be removed after development to obtain a pattern of a desired shape.
  • the Co-based organic coordination nanoparticles of the present invention are used as photoresist components to achieve more excellent lithography performances such as high resolution, high sensitivity, and low line roughness.
  • Figure 1 is a DLS particle size test chart of the purple viscous liquid prepared in Examples 1 and 14 of the present invention, wherein the left curve is the test result of Example 1, and the right curve is the test result of Example 14.
  • FIGS. 2A and 2B are chemical structure diagrams of the crystals prepared in Example 1 and Example 14 of the present invention, respectively;
  • FIG3 is an infrared spectrum test graph of the crystals prepared in Example 1 and Example 14 of the present invention.
  • 4 to 15 are exposure patterns corresponding to embodiments 2 to 13 of the present invention respectively;
  • 16 to 27 are exposure patterns corresponding to embodiments 15 to 26 of the present invention, respectively;
  • FIG. 28 is an exposure pattern of Example 27 of the present invention.
  • the present invention provides a Co-based organic coordination nanoparticle, the general formula of which is: Co m R n Q x M y N z
  • Co is two kinds of ions: divalent Co and trivalent Co;
  • R can be selected from
  • Q can be selected from imidazole and its derivatives
  • M is carboxylic acid
  • N is water of crystallization
  • the size of the Co-based organic coordination nanoparticle crystal is 1nm-5nm.
  • n, x are all greater than 0, y, z are greater than or equal to 0; further, 2 ⁇ m ⁇ 12, 4 ⁇ n ⁇ 12, 2 ⁇ x ⁇ 12, 0 ⁇ y ⁇ 18, 0 ⁇ z ⁇ 6;
  • Co-based organic coordination nanoparticles may have the following structure:
  • the Co-based organic coordination nanoparticles obtained by the present invention have a special structure, and under illumination conditions, can interact with a photoinitiator, change the polarity of the material, and agglomerate, causing the solubility of the Co-based organic coordination nanoparticles to change before and after illumination. Due to these characteristics, the Co-based organic coordination nanoparticles are used as photoresist components, and the solubility of the photosensitive part and the light-shielding part of the photoresist in the developer can be different.
  • the photosensitive part agglomerates in the developer and the solubility is reduced, while the light-shielding part does not agglomerate and dissolves in the developer, so that the non-exposed area can be removed after development to obtain a pattern of a desired shape.
  • the Co-based organic coordination nanoparticles of the present invention are used as photoresist components to achieve more excellent lithography performances such as high resolution, high sensitivity, and low line roughness.
  • Co 2 (C 7 H 7 COO) 4 (CH 3 C 2 N 2 H 3 ) 2 nanoparticles are prepared by the following method:
  • the molar ratio of the m-toluic acid or benzoic acid to cobalt acetate is in the range of 1:2 to 2:1, and the molar ratio of the m-toluic acid or benzoic acid, cobalt acetate, and 1-methylimidazole is in the range of 1:1:(1 to 3);
  • the organic solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, tetrahydrofuran, methanol, ethanol, and propanol.
  • the stirring temperature is controlled at 25-125°C, preferably 30-100°C, more preferably 30-80°C; the rotary evaporation pressure range is controlled at 70-140mBar, preferably 70-120mBar, more preferably 80-100mBar; at the same time, the rotary evaporation temperature is controlled at 30-45°C, preferably 30-40°C.
  • the present invention also provides a photoresist composition, comprising the above-mentioned Co-based organic coordination nanoparticles. Further, the above-mentioned photoresist composition also includes a photoinitiator and an organic dispersing solvent, wherein the photoinitiator preferably occupies 0.5wt%-10wt% of the composition, and the nanoparticles preferably occupy 3wt%-20wt% of the composition.
  • the photoinitiator is selected from any one or more of N-hydroxynaphthaleneimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalene disulfonic acid, tert-butylphenyl iodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.
  • the organic dispersing solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.
  • the solvent is preferably ethyl acetate.
  • the present invention also provides a method for forming a photolithographic pattern, using the above-mentioned photoresist composition, dripping the photoresist composition onto a substrate by spin coating, heating it on a hot stage, then exposing it with an electron beam or mid-ultraviolet, deep ultraviolet, or extreme ultraviolet, and developing it with a developer.
  • the spin coating speed is further controlled at 1500-2500 rpm; the heating temperature of the hot stage is controlled at 50-80° C., and the heating time is controlled at 40-120 s.
  • the exposure dose is 50 mJ/cm 2 to 500 mJ/cm 2 , and preferably the exposure dose is 150 mJ/cm 2 to 300 mJ/cm 2 .
  • the developing time may be selected to be 3-10s, preferably 3s, 5s, 7s;
  • the developer is selected from a mixture of any one or more of decahydronaphthalene, tetrahydronaphthalene, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is room temperature or 20°C to 50°C.
  • the thickness of the pre-film layer after removing the organic dispersion solvent may be 10 nm to 100 nm.
  • the thickness of the pre-film layer may be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, 90 nm to 100 nm.
  • the substrate is selected from a silicon plate.
  • Other substrates that are insoluble in the developer can also be selected according to actual needs.
  • the above nanoparticles are used in the field of photoresists, especially electron beam, mid-ultraviolet, deep ultraviolet, and extreme ultraviolet photoresists.
  • photoresists especially electron beam, mid-ultraviolet, deep ultraviolet, and extreme ultraviolet photoresists.
  • deep ultraviolet and longer wavelength light sources are transmissive masks
  • extreme ultraviolet is a reflective mask
  • the electron beam is exposed according to the pattern set by the software.
  • the molecular structure Co 12 (C 6 H 5 OO) 12 (CH 3 C 2 N 2 H 3 ) 12 (CH 3 COO) 18 (H 2 O) 6 is analyzed, as shown in FIG2A. It is a multi-nuclear complex with benzoic acid, N-methylimidazole and acetate as ligands, containing 12 Co rings, and except for N-methylimidazole, the other ligands are connected around the Co ring in the form of bridges. It can be seen that the substance prepared by the method of this embodiment is metal organic ligand nanoparticles.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated on a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 50°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer.
  • the development was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch line exposure patterns of 9.04 ⁇ m, 10.01 ⁇ m, and 10.62 ⁇ m, as shown in Figures 4, 5, and 6, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated on a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 60°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the development was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch line exposure patterns of 9.48 ⁇ m, 9.74 ⁇ m, and 9.92 ⁇ m, as shown in Figures 7, 8, and 9, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated onto a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 70°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the development was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch line exposure patterns of 9.48 ⁇ m, 10.62 ⁇ m, and 10.62 ⁇ m, as shown in Figures 10, 11, and 12, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated onto a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 80°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the development was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch line exposure patterns of 9.04 ⁇ m, 10.01 ⁇ m, and 11.06 ⁇ m, as shown in Figures 13, 14, and 15, respectively.
  • crystals can be obtained by leaving the liquid to stand at low temperature, and an infrared spectrum test is performed on it, as shown below.
  • the test results shown in FIG3 show that there is an absorption peak at 2922 cm -1 and 3130 cm -1.
  • the free m-methylbenzoic acid has an additional alkyl CH peak below 3000 cm -1 .
  • the infrared absorption spectrum of the product prepared in this embodiment also has corresponding absorption peaks near these two positions, and a slight shift occurs, which indicates that the m-methylbenzoic acid group is bonded to the metal organic compound molecular structure.
  • the substance prepared by the method of this embodiment is a metal organic ligand nanoparticle.
  • the molecular structure is shown in FIG2B, Co 2 (C 7 H 7 COO) 4 (CH 3 C 2 N 2 H 3 ) 2 .
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated onto a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 50°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the exposure was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch 1 ⁇ m line exposure patterns, as shown in Figures 16, 17, and 18, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated on a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 60°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the exposure was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch 1 ⁇ m line exposure patterns, as shown in Figures 19, 20, and 21, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated on a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 70°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the development was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch 1 ⁇ m line exposure patterns, as shown in Figures 22, 23, and 24, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated on a silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 80°C for 1 minute.
  • the above photoresist film was exposed under a 254nm ultraviolet mercury lamp with a dose of 150mJ/ cm2 , and mesitylene was used as a developer, and the exposure was performed for 3s, 5s, and 7s, respectively, to obtain half-pitch 1 ⁇ m line exposure patterns, as shown in Figures 25, 26, and 27, respectively.
  • PAG-1 N-hydroxynaphthalimide trifluoromethanesulfonate
  • the solvent was propylene glycol monoethyl ether acetate
  • the solution was spin-coated onto the silicon wafer at a speed of 2000rpm, and then heated on a hot plate at 60°C for 1 minute.
  • EBL exposure was performed, the dose was 850 ⁇ C/ cm2 , the beam intensity was 1.0-3.0A, mesitylene was used as the developer, the development time was 9s, and a half-pitch line of 100nm was obtained, as shown in Figure 28.
  • the present invention obtains a variety of effective nanoparticles and corresponding compositions, verifies the structure and has good lithography performance under mid-ultraviolet and electron beam lithography (EBL) conditions, which can achieve better lithography performance such as high resolution, high sensitivity, and low line roughness.
  • EBL electron beam lithography

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Abstract

本发明涉及一种Co基有机配位纳米颗粒及其制备方法、光刻胶组合物及其应用。本发明提供的Co基有机配位纳米颗粒，通式为：ComRnQxMyNz，其中，Co为二价Co和三价Co两种离子；R选苯甲酸基或间甲基苯甲酸基；Q可选自咪唑及其衍生物；M为羧酸；N为结晶水，所述Co基有机配位纳米颗粒晶体的尺寸为1nm-5nm。将该纳米颗粒配置成光刻胶组合物，用电子束或中紫外、深紫外、极紫外曝光、显影，可以得到高分辨、高灵敏度、低线条粗糙度的图案，本发明提供的Co基有机配位纳米颗粒及其光刻胶组合物在EUV光刻领域具有较好的应用潜力。

Description

一种Co基有机配位纳米颗粒及其制备方法、光刻胶组合物及其应用 技术领域
本发明涉及光刻胶技术领域，特别是涉及一种Co基有机配位纳米颗粒及其制备方法、光刻胶组合物及其应用。
背景技术
光刻胶(Photoresist)是指通过紫外光、电子束、粒子束、极紫外(Extreme Ultra-violet,EUV)或者软x射线等的照射，使得溶解度发生变化的耐蚀薄膜材料。随着半导体技术的不断进步以及摩尔定律的发展，半导体制程随之不断减小，对加工的特征尺寸减小提出了更高的要求。为了满足更先进的半导体制程，实现更小的特征尺寸，光刻技术也在不断发展，从I-线、G线、深紫外(Deep Ultra-violet,DUV)、193nm、浸没式193nm发展到极紫外光刻、电子束光刻等精细加工手段。光刻胶膜经过曝光显影形成光刻图形后，会进行干法或湿法刻蚀。没有胶膜覆盖的部分衬底材料被直接刻蚀，而有胶膜覆盖的衬底表面则受光刻胶膜保护而免被刻蚀。耐蚀刻性能是光刻胶非常重要的评价指标，优良的耐刻蚀性可以保障刻蚀工艺中光刻胶能保护衬底表面不受损坏，并有效的简化刻蚀工艺，大大提高刻蚀成品良率。
传统光刻胶组分复杂，包含光刻胶树脂本体、感光剂、流平剂、稳定剂、分散剂、增稠剂和溶剂等，生产制造流程繁琐，对配比和纯度的控制工艺要求极高。由于传统光刻胶多为大分子聚合物和含有众多功能化的添加剂，其成分复杂导致光刻胶尺寸分布较宽，存在各种尺寸的成分，某些尺寸构象可以达到10nm～20nm，使得光刻胶图形的尺寸难以控制，同时可能产生众多缺陷。另外，对于传统光刻胶而言，其使用范围受光源的波长影响很大，对于不同的光源需要有不同的光刻胶进行匹配。目前金属氧化物光刻胶成为研究热点，金属氧化物光刻胶成为EUV或电子束曝光极精细图案的一种可行的选择，Zn基纳米有机配体光刻胶是申请人早期研究的金属氧化物有机配体体系，并且其光刻效果也得到了实际验证。Co与Zn在周期表中位置接近，性质也有一定的相似性，有作为光刻胶的潜力，但现有对于Co基纳米有机配体光刻胶未见报道，本发明围绕该材料体系进行了深入研究，并合成出具有较好光刻效果的Co基纳米有机光刻胶组合物。
技术问题
本发明针对传统光刻胶光刻得到的图形边缘粗糙度大并且图形分辨率较低的问题，提出一种新的Co基有机配位纳米颗粒及其制备方法、包含其的光刻胶组合物及其应用。
技术解决方案
【所制备的金属有机纳米颗粒】
本发明提供一种Co基有机配位纳米颗粒，通式为：ComRnQxMyNz，其中，
Co为二价Co和三价Co两种离子；m、n、x均大于0，y、z大于等于0；
R可选自
Q可选自咪唑及其衍生物；
M为羧酸；
N为结晶水；
进一步，所述Co基有机配位纳米颗粒晶体的尺寸为1nm-5nm。
进一步，Co基有机配位纳米颗粒可以是如下结构：
Co12(C6H5COO)12(CH3C2N2H3)12(CH3COO)18(H2O)6或
Co2(C7H7COO)4(CH3C2N2H3)2。
【金属有机配位纳米颗粒的制备方法】
Co2(C7H7COO)4(CH3C2N2H3)2纳米颗粒由如下方法制备得到：
将间甲基苯甲酸或苯甲酸、醋酸钴分别加入烧瓶中，加入有机溶剂将间甲基苯甲酸或苯甲酸和醋酸钴溶解，之后再加入1-甲基咪唑，在一定温度条件下持续搅拌，在一定蒸汽压力下旋蒸得到产物。
进一步，所述间甲基苯甲酸或苯甲酸和醋酸钴的摩尔比范围为1:2～2:1，所述的间甲基苯甲酸或苯甲酸、醋酸钴、1-甲基咪唑的摩尔比范围为1：1：(1～3)。
所述有机溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、四氢呋喃、甲醇、乙醇、丙醇中的任意一种或多种。
所述的搅拌温度控制在25～125℃，优选30～100℃，更优选30～80℃；所述的旋蒸压力范围控制在70～140mBar，优选70～120mBar，更优选80～100mBar；同时，所述的旋蒸温度控制在30～45℃，优选30～40℃。
【金属有机配位纳米颗粒光刻胶】
本发明还提供了一种光刻胶组合物，包括上述Co基有机配位纳米颗粒。
进一步的，上述光刻胶组合物，还包括光引发剂和有机分散溶剂，光引发剂优选为占据组合物的0.5wt％-10wt％，纳米颗粒优选为占据组合物的3wt％-20wt％。
进一步的，光引发剂选自N-羟基萘酰亚胺三氟甲磺酸、1,4-氨基萘磺酸、2-氨基-5,7-萘二磺酸、叔丁基苯基碘鎓盐全氟辛烷磺酸、三苯基锍全氟丁烷磺酸、三苯基锍全氟丁基和三苯基锍三氟磺酸中的任意一种或多种。
进一步的，有机分散溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、甲醇、乙醇、丙醇中的任意一种或多种。溶剂优选为乙酸乙酯。
【金属有机配位纳米颗粒光刻胶图案化方法】
本发明还提供一种形成光刻图案的方法，采用上述光刻胶组合物，将光刻胶组合物以旋涂方式滴加到基板上，并在热台上加热，再用电子束或中紫外、深紫外、极紫外曝光，采用显影剂显影。
进一步所述的旋涂转速为1500～2500rpm；所述的热台加热温度控制在50～80℃，加热时间控制在40～120s。
进一步的，曝光剂量为50mJ/cm2～500mJ/cm2，优选曝光剂量为150mJ/cm2～300mJ/cm2。
进一步的，显影时间可选择3-10s，优选3s、5s、7s。
进一步的，显影剂选自十氢化萘、四氢化萘、茚、茚满、喹啉、1-甲基萘、甲苯、邻二甲苯、间二甲苯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、异丙醇、正丁醇、正己烷及环己烷中的任意一种或多种的混合物，显影温度为室温或者20℃～50℃。
除有机分散溶剂后的预成膜层的厚度可以为10nm～100nm。具体的，预成膜层的厚度可以为10nm～20nm、20nm～30nm、30nm～40nm、40nm～50nm、50nm～60nm、60nm～70nm、70nm～80nm、80nm～90nm、90nm～100nm。
所述基底选自硅板。还可根据实际需求选择其他不溶于显影剂的基底。
进一步的，上述纳米颗粒的用途，用于光刻胶领域，特别是电子束、中紫外、深紫外、极紫 外光刻胶。关于掩膜，深紫外及更长波长光源为透射掩膜，极紫外为反射掩膜，电子束根据软件所设图形曝光。
有益效果
与现有技术相比，本发明的技术方案具有以下优点：
本发明得到的Co基有机配位纳米颗粒，具有特殊结构，在光照条件下，可以和光引发剂发生相互作用，材料极性变化，发生团聚，导致Co基有机配位纳米颗粒在光照前后的溶解度发生变化。由于这些特性，将该Co基有机配位纳米颗粒作为光刻胶成分，可以使光刻胶感光部分和遮光部分在显影剂中的溶解度产生差异，感光部分团聚在显影液中溶解度降低，而遮光部分不团聚在显影液中溶解，从而显影后能够将非曝光区域去除，而获得期望形状的图案。将本发明Co基有机配位纳米颗粒作为光刻胶成分，可以实现高分辨、高灵敏度、低线条粗糙度等更优异的光刻性能。
附图说明
图1为本发明实施例1、实施例14制备的紫色粘稠液体进行DLS粒度测试图，其中左侧曲线为实施例1测试结果，右侧曲线为实施例14测试结果。
图2A和图2B分别为本发明实施例1、实施例14所制备的结晶体的化学结构图；
图3为本发明实施例1、实施例14所制备的结晶体的红外光谱测试图谱；
图4-图15分别依次为本发明实施例2-13对应的曝光图案；
图16-图27分别依次为本发明实施例15-26对应的曝光图案；
图28为本发明实施例27的曝光图案。
本发明的实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
本发明提供一种Co基有机配位纳米颗粒，通式为：ComRnQxMyNz
其中，Co为二价Co和三价Co两种离子；
R可选自
Q可选自咪唑及其衍生物；
M为羧酸；N为结晶水。
进一步，所述Co基有机配位纳米颗粒晶体的尺寸为1nm-5nm。
m、n、x均大于0，y、z大于等于0；进一步地，2≤m≤12,4≤n≤12,2≤x≤12,0≤y≤18,0≤z≤6；
进一步，Co基有机配位纳米颗粒可以是如下结构：
Co12(C6H5OO)12(CH3C2N2H3)12(CH3COO)18(H2O)6；
Co2(C7H7COO)4(CH3C2N2H3)2。
本发明得到的Co基有机配位纳米颗粒，具有特殊结构，在光照条件下，可以和光引发剂发生相互作用，材料极性变化，发生团聚，导致Co基有机配位纳米颗粒在光照前后的溶解度发生变化。由于这些特性，将该Co基有机配位纳米颗粒作为光刻胶成分，可以使光刻胶感光部分和遮光部分在显影剂中的溶解度产生差异，感光部分团聚在显影液中溶解度降低，而遮光部分不团聚在显影液中溶解，从而显影后能够将非曝光区域去除，而获得期望形状的图案。将本发明Co基有机配位纳米颗粒作为光刻胶成分，可以实现高分辨、高灵敏度、低线条粗糙度等更优异的光刻性能。
其中，Co2(C7H7COO)4(CH3C2N2H3)2纳米颗粒由如下方法制备得到：
将间甲基苯甲酸或苯甲酸、醋酸钴分别加入烧瓶中，加入有机溶剂将间甲基苯甲酸或苯甲酸和醋酸钴溶解，之后再加入1-甲基咪唑，在一定温度条件下持续搅拌，在一定蒸汽压力下旋蒸得到产物。
进一步，所述的间甲基苯甲酸或苯甲酸和醋酸钴的摩尔比范围为1:2～2:1，所述的间甲基苯甲酸或苯甲酸、醋酸钴、1-甲基咪唑的摩尔比范围为1：1：(1～3)；
所述的有机溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、四氢呋喃、甲醇、乙醇、丙醇中的任意一种或多种。
所述的搅拌温度控制在25～125℃，优选30～100℃，更优选30～80℃；所述的旋蒸压力范围控制在70～140mBar，优选70～120mBar，更优选80～100mBar；同时，所述的旋蒸温度控制在30～45℃，优选30～40℃。
本发明还提供了一种光刻胶组合物，包括上述Co基有机配位纳米颗粒。进一步的，上述光刻胶组合物，还包括光引发剂和有机分散溶剂，光引发剂优选为占据组合物的0.5wt％-10wt％，纳米颗粒优选为占据组合物的3wt％-20wt％。
进一步的，光引发剂选自N-羟基萘酰亚胺三氟甲磺酸、1,4-氨基萘磺酸、2-氨基-5,7-萘二磺酸、叔丁基苯基碘鎓盐全氟辛烷磺酸、三苯基锍全氟丁烷磺酸、三苯基锍全氟丁基和三苯基锍三氟磺酸中的任意一种或多种。
进一步的，有机分散溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、甲醇、乙醇、丙醇中的任意一种或多种。溶剂优选为乙酸乙酯。
本发明还提供一种形成光刻图案的方法，采用上述光刻胶组合物，将光刻胶组合物以旋涂方式滴加到基板上，并在热台上加热，再用电子束或中紫外、深紫外、极紫外曝光，采用显影剂显影。
进一步所述的旋涂转速为1500～2500rpm；所述的热台加热温度控制在50～80℃，加热时间控制在40～120s。
进一步的，曝光剂量为50mJ/cm2～500mJ/cm2，优选曝光剂量为150mJ/cm2～300mJ/cm2。
进一步的，显影时间可选择3-10s，优选3s、5s、7s；
进一步的，显影剂选自十氢化萘、四氢化萘、茚、茚满、喹啉、1-甲基萘、甲苯、邻二甲苯、间二甲苯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、异丙醇、正丁醇、正己烷及环己烷中的任意一种或多种的混合物，显影温度为室温或者20℃～50℃。
除有机分散溶剂后的预成膜层的厚度可以为10nm～100nm。具体的，预成膜层的厚度可以为10nm～20nm、20nm～30nm、30nm～40nm、40nm～50nm、50nm～60nm、60nm～70nm、70nm～80nm、80nm～90nm、90nm～100nm。
所述基底选自硅板。还可根据实际需求选择其他不溶于显影剂的基底。
进一步的，上述纳米颗粒的用途，用于光刻胶领域，特别是电子束、中紫外、深紫外、极紫外光刻胶。关于掩膜，深紫外及更长波长光源为透射掩膜，极紫外为反射掩膜，电子束根据软件所设图形曝光。
实施例1
将4.88g(40mmol)苯甲酸和4.98g(20mmol)醋酸钴分别加入100mL烧瓶中，加入45mL四氢呋喃。加入1.67～2.30g(20～28mmol)1-甲基咪唑在25～125℃下搅拌加热24小时。产物在70～140mBar，30～45℃下旋蒸20～40分钟，得到紫色粘稠液体，对于得到的产物进行DLS粒度测试，结果如图1中左侧曲线所示，可以看出，所制备的体系是纳米颗粒(平均粒径3.1nm)。进一步，将液体在低温下静置可以得到结晶体，对其进行红外光谱测试，得到如图3所示的测试结果，可以看出，在3130cm-1有一个吸收峰，该吸收峰是键连后的芳环吸收峰，因为，游离的苯甲酸红外吸收峰位于3000～3100cm-1之间，对应于苯甲酸基团的苯环不饱和＝C-H的伸缩振动，也就是说合成的Co基有机配体结构物质中发生了与苯甲酸吸收峰位置的微小偏移，这样说明苯甲酸基团键联到金属有机化合物分子结构上。配合核磁共振分析结果，解析出分子结构Co12(C6H5OO)12(CH3C2N2H3)12(CH3COO)18(H2O)6，如图2A所示。其为以苯甲酸、N-甲基咪唑、醋酸根为配体，含有12个Co环形的多核配合物，除N-甲基咪唑外，其余配体均以桥连的形式接在Co环的四周。可见，通过本实施例的方法制备得到的物质为金属有机配体纳米颗粒。
实施例2-4
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例1中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在50℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为9.04μm、10.01μm、10.62μm线条曝光图案，分别见图4、5、6。
实施例5-7
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例1中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在60℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为9.48μm、9.74μm、9.92μm线条曝光图案，分别见图7、8、9。
实施例8-10
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例1中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在70℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为9.48μm、10.62μm、10.62μm线条曝光图案，分别见图10、11、12。
实施例11-13
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例1中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在80℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为9.04μm、10.01μm、11.06μm线条曝光图案，分别见图13、14、15。
实施例14
将5.44g(40mmol)间甲基苯甲酸和4.98g(20mmol)醋酸钴分别加入100mL烧瓶中，加入45mL四氢呋喃。加入1.67～2.30g(20～28mmol)1-甲基咪唑在25～125℃下搅拌加热24小时。产物在70～140mBar，30～45℃下旋蒸20～40分钟，得到紫色粘稠液体。对产物进行DLS粒度测试，结果如图1右侧曲线所示，可以看出，所制备的体系是纳米颗粒(平均粒径4.3nm)。进一步，将液体在低温下静置可以得到结晶体，对其进行红外光谱测试，得到如 图3所示的测试结果，可以看出，在2922cm-1、3130cm-1均有一个吸收峰，游离的间甲基苯甲酸除了在3000～3100cm-1之间有一个对应于苯甲酸基团的苯环不饱和＝C-H的伸缩振动吸收峰之外，在3000cm-1以下会有一个额外的烷基C-H峰，而本实施例所制备的产物的红外吸收光谱也在这两个位置附近有对应的吸收峰，并且发生了微小偏移，这样说明间甲基苯甲酸基团键联到金属有机化合物分子结构上。通过本实施例的方法制备得到的物质为金属有机配体纳米颗粒。分子结构如图2B所示，Co2(C7H7COO)4(CH3C2N2H3)2。
实施例15-17
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例14中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在50℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为1μm线条曝光图案，分别见图16、17、18。
实施例18-20
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例14中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在60℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为1μm线条曝光图案，分别见图19、20、21。
实施例21-23
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例14中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在70℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为1μm线条曝光图案，分别见图22、23、24。
实施例24-26
0.5wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例14中的所制备的溶液中(5.0wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在80℃的热台上加热1分钟。将上述光刻胶膜在254nm紫外汞灯下曝光，剂量为150mJ/cm2，用均三甲苯为显影剂，分别显影3s、5s、7s，得到half-pitch为1μm线条曝光图案，分别见图25、26、27。
实施例27
10wt％PAG-1(N-羟基萘酰亚胺三氟甲磺酸酯)加入到实施例14中的所制备的溶液中(3.5wt％)，溶剂为丙二醇单乙醚醋酸酯，以2000rpm的转速旋涂到硅片上，后在60℃的热台上加热1分钟。进行EBL曝光，剂量为850μC/cm2，束流强度1.0～3.0A，用均三甲苯做显影剂，显影时间为9s，得到half-pitch为100nm线条，见图28。
综上，本发明获得了多种有效的纳米颗粒以及相应的组合物，验证了结构和中紫外下以及电子束光刻(EBL)条件下具备良好的光刻性能，其可以实现高分辨、高灵敏度、低线条粗糙度等更优异的光刻性能。

Claims (13)

  1. 一种Co基有机配位纳米颗粒，其特征在于，组成通式为：ComRnQxMyNz，其中，Co为二价Co和三价Co两种离子；m、n、x均大于0，y、z大于等于0；
    R可选自
    Q可选自咪唑及其衍生物；
    M为羧酸；
    N为结晶水；
    所述Co基有机配位纳米颗粒晶体的尺寸为1nm-5nm。
  2. 根据权利要求1所述的Co基有机配位纳米颗粒，其特征在于，所述纳米颗粒结构为Co12(C6H5COO)12(CH3C2N2H3)12(CH3COO)18(H2O)6或Co2(C7H7COO)4(CH3C2N2H3)2。
  3. 根据权利要求1或2所述的Co基有机配位纳米颗粒的制备方法，其特征在于，具体包括以下步骤：将间甲基苯甲酸或苯甲酸、醋酸钴分别加入烧瓶中，加入有机溶剂将所述间甲基苯甲酸或苯甲酸和所述醋酸钴溶解，之后再加入1-甲基咪唑，在一定温度条件下持续搅拌，在一定蒸汽压力下旋蒸得到产物。
  4. 根据权利要求3所述的Co基有机配位纳米颗粒的制备方法，其特征在于：所述间甲基苯甲酸或苯甲酸和所述醋酸钴的摩尔比范围为0.5～2，所述间甲基苯甲酸或苯甲酸：醋酸钴：1-甲基咪唑的摩尔比范围为1：1：(1～3)。
  5. 根据权利要求3所述的Co基有机配位纳米颗粒的制备方法，其特征在于：所述有机溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、四氢呋喃、甲醇、乙醇、丙醇中的任意一种或多种。
  6. 根据权利要求3所述的Co基有机配位纳米颗粒的制备方法，其特征在于：搅拌温度控制在25～125℃，旋蒸压力范围控制在70～140mBar，旋蒸温度控制在30～45℃。
  7. 一种光刻胶组合物，包括如权利要求1或2所述的Co基有机配位纳米颗粒，光引发剂 和有机分散溶剂，所述光引发剂占据组合物的0.5wt％-10wt％，纳米颗粒占据组合物的3wt％-20wt％。
  8. 根据权利要求7所述的光刻胶组合物，其特征在于：所述光引发剂选自N-羟基萘酰亚胺三氟甲磺酸、1,4-氨基萘磺酸、2-氨基-5,7-萘二磺酸、叔丁基苯基碘鎓盐全氟辛烷磺酸、三苯基锍全氟丁烷磺酸、三苯基锍全氟丁基和三苯基锍三氟磺酸中的任意一种或多种。
  9. 根据权利要求7所述的光刻胶组合物，其特征在于：所述有机分散溶剂选自乙酸乙酯、乙酸丁酯、丙二醇单乙醚醋酸酯、丙二醇甲醚醋酸酯、1-乙氧基-2丙醇、甲醇、乙醇、丙醇中的任意一种或多种。
  10. 一种形成光刻图案的方法，其特征在于采用如权利要求7-9任一项所述的光刻胶组合物，将所述光刻胶组合物以旋涂方式滴加到基板上，并在热台上加热，再用电子束或中紫外、深紫外、极紫外曝光，采用显影剂显影，旋涂转速为1500～2500rpm；热台加热温度控制在50～80℃，加热时间控制在40～120s，曝光剂量为50mJ/cm2～500mJ/cm2，显影时间3-10s。
  11. 根据权利要求10所述的形成光刻图案的方法，其特征在于，所述显影剂选自十氢化萘、四氢化萘、茚、茚满、喹啉、1-甲基萘、甲苯、邻二甲苯、间二甲苯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、异丙醇、正丁醇、正己烷及环己烷中的任意一种或多种的混合物，显影温度为室温或者20℃～50℃。
  12. 根据权利要求10所述的形成光刻图案的方法，其特征在于，除有机分散溶剂后的预成膜层的厚度可以为10nm～100nm。
  13. 权利要求1或2所述的Co基有机配位纳米颗粒的用途，主要用于电子束、中紫外、深紫外或极紫外光刻胶。
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